JPS6247912B2 - - Google Patents
Info
- Publication number
- JPS6247912B2 JPS6247912B2 JP59044910A JP4491084A JPS6247912B2 JP S6247912 B2 JPS6247912 B2 JP S6247912B2 JP 59044910 A JP59044910 A JP 59044910A JP 4491084 A JP4491084 A JP 4491084A JP S6247912 B2 JPS6247912 B2 JP S6247912B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- antifouling
- paint composition
- metal selected
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 230000003373 anti-fouling effect Effects 0.000 claims description 49
- 239000003973 paint Substances 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 38
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- -1 thiurams Chemical class 0.000 claims description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 239000012990 dithiocarbamate Substances 0.000 claims description 3
- 150000004659 dithiocarbamates Chemical class 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 229920002379 silicone rubber Polymers 0.000 claims description 3
- 239000004945 silicone rubber Substances 0.000 claims description 3
- 150000003606 tin compounds Chemical class 0.000 claims description 3
- 239000002966 varnish Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 2
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 239000013535 sea water Substances 0.000 description 9
- 239000002519 antifouling agent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 239000008199 coating composition Substances 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 2
- SBXWFLISHPUINY-UHFFFAOYSA-N triphenyltin Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)C1=CC=CC=C1 SBXWFLISHPUINY-UHFFFAOYSA-N 0.000 description 2
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical compound NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- YYNNRJWNBXEQTP-UHFFFAOYSA-N 2-[(4-bromophenyl)sulfonylamino]-3-phenylpropanoic acid Chemical compound C=1C=C(Br)C=CC=1S(=O)(=O)NC(C(=O)O)CC1=CC=CC=C1 YYNNRJWNBXEQTP-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- WDQNIWFZKXZFAY-UHFFFAOYSA-M fentin acetate Chemical compound CC([O-])=O.C1=CC=CC=C1[Sn+](C=1C=CC=CC=1)C1=CC=CC=C1 WDQNIWFZKXZFAY-UHFFFAOYSA-M 0.000 description 1
- NJVOZLGKTAPUTQ-UHFFFAOYSA-M fentin chloride Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 NJVOZLGKTAPUTQ-UHFFFAOYSA-M 0.000 description 1
- BFWMWWXRWVJXSE-UHFFFAOYSA-M fentin hydroxide Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(O)C1=CC=CC=C1 BFWMWWXRWVJXSE-UHFFFAOYSA-M 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- BLCKKNLGFULNRC-UHFFFAOYSA-L n,n-dimethylcarbamodithioate;nickel(2+) Chemical compound [Ni+2].CN(C)C([S-])=S.CN(C)C([S-])=S BLCKKNLGFULNRC-UHFFFAOYSA-L 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- DFNPRTKVCGZMMC-UHFFFAOYSA-M tributyl(fluoro)stannane Chemical compound CCCC[Sn](F)(CCCC)CCCC DFNPRTKVCGZMMC-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
本発明は、水中防汚塗料組成物に関する。さら
に詳しくは、船底、水中構造物（港湾施設、石油
掘さく装置、魚貝類養殖用生簣の金網及び支柱、
橋脚等、海水あるいは淡水中で使用される構造
物）あるいは海水導入管等に適用可能な銅合金粉
末を含有する水中防汚塗料組成物に関する。
一般に、船舶においては、その底部外板に海洋
生物が付着すると、推進エネルギーの浪費をもた
らし、船舶の運航に支障をきたすようになること
が知られている。また海洋構造物においては、そ
の表面に生物が付着し、防食被覆層が損傷し、そ
の結果構造物の耐用年数が著しく短くなることが
分つている。さらに海水導入管等においても付着
生物の堆積により、その本来の機能が著しく低下
する等の問題があつた。
このように海洋生物の付着は、産業上極めて大
きな損害をもたらすため、その付着は、極力避け
なければならず、その対策として各種防汚剤を配
合した水中防汚塗料組成物が使用されている。
ところで従来の防汚塗料組成物は、例えば塩化
ビニル樹脂等の被膜形成可能な耐水性樹脂を展色
剤とし、これに亜酸化銅、ロダン銅等の銅化合物
もしくは銅金属、あるいは有機錫化合物等の防汚
剤を添加した組成物、又は更に防汚剤の溶出助剤
等を添加した塗料組成物からなるものである。し
かしてこの種の塗料組成物から得られた塗膜の防
汚性は、塗料中に含まれる防汚剤又はその分解生
成物が塗膜から海水中等へ徐々に溶出、拡散する
ことにより発揮されるものである。
また、近年防汚成分を被膜形成樹脂と化学的に
結合させたものを主成分とする、有機錫ポリマー
タイプの防汚塗料組成物が使用されるようになつ
て来た。しかしてこの種の塗料組成物から形成さ
れた塗膜は、海水中で徐々に加水分解反応をおこ
し、防汚剤が海水中に放出されて防汚効果を発揮
すると同時に、加水分解後の皮膜形成樹脂も水可
溶性となり、塗膜自体が海水に徐々に溶解し、付
着生物とともに剥離していくというメカニズムか
らなるものである。
さらに、近年船舶、海洋構造物あるいは海水導
入管等の分野においては、その塗り替え作業が著
しく困難であるため、一度塗布したら、より長期
の防汚効果が期待できる塗膜を形成し得る防汚塗
料組成物に対する要求が非常に強くなつて来てい
る。
加うるに、従来の防汚塗料組成物は、往々にし
て貯蔵時に増粘する傾向があり、著しい場合には
塗布が殆ど不可能になるというような問題点があ
つた。それ故このような塗料組成物の各種欠点の
改良が強く望まれていたのである。
本発明者等は、かかる実情に鑑み、優れた貯蔵
安定性とともに優れた防汚性能を有し、かつその
防汚効果をより長期間持続することのできる塗膜
を形成し得る、水中防汚塗料組成物につき鋭意研
究の結果、本発明に到達した。
つまり、本発明の目的は、極めて良好な貯蔵安
定性と優れた防汚性能を有し、かつその防汚効果
を長期間にわたり持続できるような塗膜を形成し
得る水中防汚塗料組成物を提供することにある。
即ち、本発明は、(イ)展色剤、(ロ)ニツケル及びマ
ンガンから選ばれた金属の少なくとも一種を３〜
25重量％、亜鉛及び錫から選ばれた金属の少なく
とも一種を0.1〜５重量％、及びアルミニウム及
びシリコンから選ばれた金属の少なくとも一種を
0.1〜１重量％含有する銅合金粉末、及びさらに
別の態様として前記(イ)、(ロ)に加え、(ハ)有機錫化合
物、チウラム類及びジチオカルバミン酸塩から選
ばれた少なくとも一種の化合物（以下、化合物(ハ)
という）を含有することからなる水中防汚塗料組
成物に関する。
本発明の水中防汚塗料組成物に使用される前記
「展色剤」としては、通常防汚塗料組成物の展色
剤として使用されているものが全て支障なく使用
できる。例えば、ビニル樹脂（塩化ビニル樹脂、
塩化ビニル−イソブチルエーテル共重合体樹脂、
塩化ビニル−酢酸ビニル共重合体樹脂等）、塩化
ゴム樹脂、塩素化ポリエチレン、塩素化ポリプロ
ピレン、アクリル樹脂、スチレン−ブタジエン共
重合体樹脂、エポキシ樹脂、マレイン化ジシクロ
ペンタジエン樹脂、油ワニス、ロジン、トリブチ
ル錫含有アクリルコポリマーやトリフエニル錫含
有アクリルコポリマー等の有機錫含有ポリマー、
あるいはシリコンゴム等が好適に使用可能であ
る。
これらは必要により一種もしくは二種以上の混
合物として使用される。
叉、本発明の水中防汚塗料組成物に使用される
防汚剤としての銅合金粉末は、ニツケル及びマン
ガンから選ばれた金属の少なくとも一種を３〜25
重量％、亜鉛及び錫から選ばれた金属の少なくと
も一種を0.1〜５重量％、アルミニウム及びシリ
コンから選ばれた金属の少なくとも一種を0.1〜
１重量％含有し、残りの組成は銅を主成分とする
ものである。
銅合金粉末製造時に使用する原料に通常由来す
る不可避金属不純物の混入した組成物も本発明の
技術的範囲に含まれるものとする。
本発明で言う銅合金粉末の形状は、粒状、繊維
状もしくは扁平状等の粉末全てを包含する。
前記銅合金粉末において、ニツケル及びマンガ
ンから選ばれた少なくとも一種の金属の含有量が
３重量％にみたない場合には、銅合金粉末が酸化
する傾向が大きくなり、従つて防汚効果の持続性
が期待出来なくなる。しかも、水中浸漬初期にお
いては、銅イオンの溶出量が過剰となり、結果的
には塗膜の防汚効果の持続性が低下するようにな
る。
一方、前記銅合金粉末において、亜鉛及び錫か
ら選ばれた少なくとも一種の金属の含有量が0.1
重量％より少ない場合には、銅合金の組織の均一
化が実現されず、銅イオンの均一な溶解が損なわ
れ、銅合金の浪費を招き、結果的には塗膜の防汚
効果の持続性が低下するようになる。
さらに、前記銅合金粉末において、アルミニウ
ム及びシリコンから選ばれた少なくとも一種の金
属の含有量が0.1重量％にみたない場合には、銅
イオンの均一な溶出が困難となり、叉脱酸効果も
期待しにくく、結果的には防汚効果の持続性が低
下するようになる。
逆に、ニツケル及びマンガンから選ばれた金属
の少なくとも１種の含有量が25重量％をこえる
と、必然的に防汚剤としての銅含有量が少なくな
り、叉、亜鉛及び錫から選ばれた金属の少なくと
も一種の含有量が５重量％をこえた場合及びアル
ミニウム及びシリコンから選ばれた金属の少なく
とも１種の含有量が１重量％をこえると銅の溶出
効果による殺菌効果が抑制され、いずれの場合も
防汚効果が低下する。
また前記銅合金粉末は、塗膜の表面状態等を考
慮して、平均粒子径10μ以下の粒状、又は平均長
さ10〜200μ、平均厚さ２〜10μ程度の扁平状粒
子、もしくは平均径２〜15μ、平均長さ10〜200
μ程度の繊維状であることが好ましい。
いずれにしても本発明における銅合金粉末は前
記の如き特定の組成にすることにより銅イオンの
溶出をコントロールし、防汚効果の持続性をもた
せることが出来るのである。
本発明の第１の態様においては、前記銅合金粉
末は展色剤固形分100重量部に対して100〜950重
量部、好ましくは200〜900重量部の割合で使用す
ることが好ましい。
前記範囲において、銅合金粉末の使用量が100
重量部にみたない場合には、目的とする防汚効果
が発揮されにくい。一方、950重量部をこえて使
用されると塗膜強度が低下し易く、ハガレ等の欠
陥を生起し易くなるのであまり好ましくない。
本発明の水中防汚塗料組成物は、それだけで十
分防汚性を有する塗膜を形成し得るが、更に防汚
性や防藻性等の向上をはかる場合には、必要に応
じて、例えばトリブチル錫フルオライド、ビスト
リブチル錫オキサイド、トリブチル錫クロライ
ド、ビス（トリブチル錫）−α−α′−ジブロムサ
クシネート、トリフエニル錫ハイドロオキサイ
ド、トリフエニル錫アセテート、トリフエニル錫
クロライド、トリフエニル錫フルオライド、ビス
（トリフエニル錫）−α−α′−ジブロムサクシネ
ート、トリフエニル錫ニコチン酸等の有機錫化合
物；テトラメチルチウラムジサルフアイド、ビス
（ジメチルチオカルバモイル）ジスルフオイド等
のチウラム類；ジメチルジチオカルバミド酸ニツ
ケル、ジメチルジチオカルバミド酸亜鉛等のジチ
オカルバミン酸塩から選ばれた少なくとも一種の
化合物等（化合物(ハ)）を、併用してもよい。
即ち、本発明の第２の態様の組成物は、展色剤
固形分100重量部に対して、前記銅合金粉末100〜
800重量部、及び化合物(ハ)250重量部以下の割合か
ら成るものである。
前記化合物(ハ)の範囲において、その量が250重
量部をこえて使用されると、塗膜の強度が低下す
る傾向を示すため好ましくない。
本発明の水中防汚塗料組成物においては、前記
成分の他に、必要により着色顔料；体質顔料；可
塑剤；防汚剤の溶出助剤（ロジン等）；溶剤；そ
の他各種添加剤（発泡防止剤、沈降防止剤、レベ
リング剤）など、通常塗料に使用されている各種
成分を添加混合し得る。
本発明の水中防汚塗料組成物は、展色剤、銅合
金粉末（および化合物(ハ)）を通常の塗料製造装置
（ボールミル、デイスパー等）にて一括もしくは
分割混合分散することにより一液型塗料として調
製することができる。
また、塗料成分を二液型に分けて使用直前に混
合分散して調製してもよい。
かくして調製された本発明の水中防汚塗料組成
物は、そのまま、もしくは溶剤で粘度調整した
後、通常はエアレススプレー塗装により、場合に
よつてはローラー塗装、刷毛塗り、二頭ガン塗装
により、船舶や水洋構造物等に約30μ〜300μの
乾燥膜厚で適用する。
前述の如き構成からなる本発明の水中防汚塗料
組成物から得られた塗膜は、防汚性に優れ、しか
もその防汚性能を長期間にわたり維持することが
可能である。
以下、本発明の詳細を実施例及び比較例にて説
明する。「部」又は「％」は「重量部」又は「重
量％」である。
実施例１〜24及び比較例１〜10
第１表及び第２表に示した配合により本発明及
び比較例の防汚塗料組成物を得た。まず実施例１
〜24及び比較例８〜10においては、銅合金粉末を
除いた成分を混合し、ポツトミルで一昼夜練合し
た後、銅合金粉末をデイスパーにより撹拌混合し
た。また比較例１〜７においては、全成分を混合
し、ポツトミルで一昼夜練合して塗料組成物を得
た。尚、各防汚塗料組成物の貯蔵安定性及び各塗
料組成物から得られた塗膜の防汚性の比較試験結
果は第３表に示した。
The present invention relates to an underwater antifouling coating composition. More specifically, ship bottoms, underwater structures (port facilities, oil drilling equipment, wire nets and supports for fish and shellfish cultivation, etc.)
The present invention relates to an underwater antifouling paint composition containing copper alloy powder that can be applied to structures used in seawater or freshwater, such as bridge piers, or seawater introduction pipes. In general, it is known that when marine organisms adhere to the bottom shell of a ship, it results in a waste of propulsion energy and causes trouble in the operation of the ship. Furthermore, it has been found that organisms adhere to the surface of marine structures, damaging the anticorrosive coating layer, and as a result, the service life of the structure is significantly shortened. Furthermore, there have been problems such as the accumulation of attached organisms on seawater inlet pipes, etc., which significantly deteriorates their original functions. In this way, the adhesion of marine organisms causes extremely great damage industrially, so it must be avoided as much as possible, and as a countermeasure, underwater antifouling paint compositions containing various antifouling agents are used. . By the way, conventional antifouling paint compositions use a water-resistant resin capable of forming a film, such as vinyl chloride resin, as a color vehicle, and add a copper compound or metal such as cuprous oxide or copper rhodan, or an organic tin compound, etc. It consists of a composition to which an antifouling agent is added, or a coating composition to which an elution aid for the antifouling agent is added. However, the antifouling property of the paint film obtained from this type of paint composition is achieved by the gradual elution and diffusion of the antifouling agent contained in the paint or its decomposition products from the paint film into seawater, etc. It is something that Furthermore, in recent years, organic tin polymer type antifouling paint compositions, which contain as a main component an antifouling component chemically bonded to a film-forming resin, have come into use. However, the paint film formed from this type of paint composition gradually undergoes a hydrolysis reaction in seawater, and the antifouling agent is released into the seawater and exhibits an antifouling effect. The mechanism is that the forming resin also becomes water-soluble, and the coating itself gradually dissolves in seawater and peels off along with the attached organisms. Furthermore, in recent years, it has become extremely difficult to repaint vessels, offshore structures, or seawater inlet pipes, so once applied, antifouling paints can form a film that can be expected to have a long-term antifouling effect. The demands on compositions are becoming very strong. In addition, conventional antifouling paint compositions often tend to thicken during storage, and in severe cases, they have the problem of becoming almost impossible to coat. Therefore, it has been strongly desired to improve the various drawbacks of such coating compositions. In view of these circumstances, the present inventors have developed an underwater antifouling film that can form a coating film that has excellent storage stability and antifouling performance and can maintain its antifouling effect for a longer period of time. As a result of extensive research into paint compositions, we have arrived at the present invention. In other words, the object of the present invention is to provide an underwater antifouling paint composition that has extremely good storage stability and excellent antifouling performance, and is capable of forming a coating film that can maintain its antifouling effect for a long period of time. It is about providing. That is, the present invention provides (a) a color vehicle, and (b) at least one metal selected from nickel and manganese.
25% by weight, 0.1 to 5% by weight of at least one metal selected from zinc and tin, and at least one metal selected from aluminum and silicon.
Copper alloy powder containing 0.1 to 1% by weight, and in another embodiment, in addition to the above (a) and (b), (c) at least one compound selected from organotin compounds, thiurams, and dithiocarbamates ( Below, compound (c)
). As the "color vehicle" used in the underwater antifouling paint composition of the present invention, all those commonly used as color vehicles in antifouling paint compositions can be used without any problem. For example, vinyl resin (vinyl chloride resin,
Vinyl chloride-isobutyl ether copolymer resin,
vinyl chloride-vinyl acetate copolymer resin, etc.), chlorinated rubber resin, chlorinated polyethylene, chlorinated polypropylene, acrylic resin, styrene-butadiene copolymer resin, epoxy resin, maleated dicyclopentadiene resin, oil varnish, rosin, Organotin-containing polymers such as tributyltin-containing acrylic copolymers and triphenyltin-containing acrylic copolymers;
Alternatively, silicone rubber or the like can be suitably used. These may be used singly or as a mixture of two or more, if necessary. Further, the copper alloy powder as an antifouling agent used in the underwater antifouling paint composition of the present invention contains at least one metal selected from nickel and manganese in an amount of 3 to 25%.
0.1-5% by weight of at least one metal selected from zinc and tin, 0.1-5% by weight of at least one metal selected from aluminum and silicon.
It contains 1% by weight, and the remaining composition is mainly copper. Compositions containing unavoidable metal impurities normally derived from raw materials used in the production of copper alloy powder are also included within the technical scope of the present invention. The shape of the copper alloy powder referred to in the present invention includes all types of powder such as granular, fibrous, and flat. If the content of at least one metal selected from nickel and manganese is less than 3% by weight in the copper alloy powder, the tendency of the copper alloy powder to oxidize increases, and the sustainability of the antifouling effect is therefore reduced. can no longer be expected. Moreover, at the initial stage of immersion in water, the amount of copper ions eluted becomes excessive, and as a result, the durability of the antifouling effect of the coating film decreases. On the other hand, in the copper alloy powder, the content of at least one metal selected from zinc and tin is 0.1
If it is less than % by weight, the structure of the copper alloy will not be made uniform, the uniform dissolution of copper ions will be impaired, the copper alloy will be wasted, and as a result, the durability of the antifouling effect of the coating film will be affected. starts to decrease. Furthermore, if the content of at least one metal selected from aluminum and silicon is less than 0.1% by weight in the copper alloy powder, it will be difficult to uniformly elute copper ions, and a deoxidizing effect may not be expected. As a result, the durability of the antifouling effect decreases. Conversely, if the content of at least one metal selected from nickel and manganese exceeds 25% by weight, the content of copper as an antifouling agent will inevitably decrease, and the content of at least one metal selected from zinc and tin will inevitably decrease. If the content of at least one metal exceeds 5% by weight, or if the content of at least one metal selected from aluminum and silicon exceeds 1% by weight, the bactericidal effect due to copper elution will be suppressed, and eventually In this case, the antifouling effect also decreases. In addition, the copper alloy powder may be granular with an average particle size of 10μ or less, or flat particles with an average length of 10 to 200μ and an average thickness of about 2 to 10μ, or an average diameter of 2 to 10μ, depending on the surface condition of the coating film. ~15μ, average length 10~200
It is preferable to have a fibrous shape of about μ. In any case, by making the copper alloy powder in the present invention have a specific composition as described above, the elution of copper ions can be controlled and the antifouling effect can be maintained for a long time. In the first aspect of the present invention, the copper alloy powder is preferably used in an amount of 100 to 950 parts by weight, preferably 200 to 900 parts by weight, based on 100 parts by weight of the solid content of the vehicle. In the above range, the amount of copper alloy powder used is 100
If it is not calculated by weight, it is difficult to achieve the desired antifouling effect. On the other hand, if more than 950 parts by weight is used, the strength of the coating film tends to decrease and defects such as peeling tend to occur, which is not so preferred. The underwater antifouling paint composition of the present invention can form a coating film having sufficient antifouling properties by itself, but if it is desired to further improve the antifouling properties and antialgae properties, for example, Tributyltin fluoride, bistributyltin oxide, tributyltin chloride, bis(tributyltin)-α-α′-dibromsuccinate, triphenyltin hydroxide, triphenyltin acetate, triphenyltin chloride, triphenyltin fluoride, bis(triphenyltin) )-α-α′-dibromusuccinate, organotin compounds such as triphenyltinnicotinic acid; thiurams such as tetramethylthiuram disulfide, bis(dimethylthiocarbamoyl)disulfoid; nickel dimethyldithiocarbamate, dimethyldithiocarbamide At least one compound selected from dithiocarbamates such as zinc oxide (compound (c)) may be used in combination. That is, the composition of the second aspect of the present invention contains 100 to 100 parts by weight of the copper alloy powder per 100 parts by weight of the solid content of the vehicle.
800 parts by weight, and 250 parts by weight or less of compound (c). If the amount of compound (c) exceeds 250 parts by weight, the strength of the coating film tends to decrease, which is not preferable. In the underwater antifouling paint composition of the present invention, in addition to the above-mentioned components, if necessary, color pigments; extender pigments; plasticizers; elution aids for antifouling agents (rosin, etc.); solvents; and other various additives (foaming prevention It is possible to add and mix various components commonly used in paints, such as anti-settling agents, anti-settling agents, and leveling agents. The underwater antifouling paint composition of the present invention can be made into a one-component type by mixing and dispersing the color vehicle, copper alloy powder (and compound (c)) all at once or in parts using ordinary paint manufacturing equipment (ball mill, disper, etc.). Can be prepared as a paint. Alternatively, the coating components may be prepared by dividing them into a two-component type and mixing and dispersing them immediately before use. The underwater antifouling paint composition of the present invention thus prepared is applied to a ship as it is, or after adjusting the viscosity with a solvent, usually by airless spray coating, or in some cases by roller coating, brush coating, or double gun coating. Applicable to dry film thickness of approximately 30μ to 300μ for water and ocean structures. The coating film obtained from the underwater antifouling paint composition of the present invention having the above-mentioned structure has excellent antifouling properties and can maintain its antifouling properties for a long period of time. The details of the present invention will be explained below using Examples and Comparative Examples. "Parts" or "%" are "parts by weight" or "% by weight." Examples 1 to 24 and Comparative Examples 1 to 10 Antifouling coating compositions of the present invention and comparative examples were obtained according to the formulations shown in Tables 1 and 2. First, Example 1
-24 and Comparative Examples 8-10, the components except the copper alloy powder were mixed and kneaded in a pot mill all day and night, and then the copper alloy powder was stirred and mixed with a disper. In Comparative Examples 1 to 7, all the components were mixed and kneaded in a pot mill for a day and night to obtain coating compositions. Table 3 shows the comparative test results of the storage stability of each antifouling paint composition and the antifouling properties of the coating film obtained from each paint composition.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
前記第３表の比較試験結果から明らかなよう
に、塗膜の海水浸漬試験（18ヶ月間）では、本発
明の防汚塗料組成物の塗膜にはわずかな生物付着
以外異常は認められず、本発明の防汚塗料組成物
は非常に優れた防汚性能を有するものであり、更
に、本発明の防汚塗料組成物は、比較例の塗料組
成物に比して貯蔵安定性（50℃、30日間）が著し
く優れたものであることが分かる。特に増粘し易
い有機錫含有共重合体を展色剤とした時の効果は
著しいものである。[Table] As is clear from the comparative test results in Table 3 above, in the seawater immersion test (18 months) of the paint film, there were no abnormalities other than slight biofouling on the paint film of the antifouling paint composition of the present invention. The antifouling paint composition of the present invention has very excellent antifouling performance, and furthermore, the antifouling paint composition of the present invention has better storage stability than the paint composition of the comparative example. It can be seen that the properties (50°C, 30 days) are significantly superior. In particular, when an organic tin-containing copolymer that easily thickens is used as a color vehicle, the effect is remarkable.
Claims (1)
ばれた金属の少なくとも一種を３〜25重量％、亜
鉛及び錫から選ばれた金属の少なくとも一種を
0.1〜５重量％、及びアルミニウム及びシリコン
から選ばれた金属の少なくとも一種を0.1〜１重
量％含有する銅合金粉末とからなる水中防汚塗料
組成物。 ２ 展色剤は、ビニル樹脂、塩化ゴム樹脂、シリ
コンゴム、油性ワニス、ロジン、有機錫化合物含
有ポリマーから選ばれた少なくとも一種である特
許請求の範囲第１項記載の水中防汚塗料組成物。 ３ 展色剤（固形分）100重量部に対し、銅合金
粉末100〜950重量部の割合からなる特許請求の範
囲第１項又は第２項記載の水中防汚塗料組成物。 ４ (イ)展色剤、(ニ)ニツケル及びマンガンから選ば
れた金属の少なくとも一種を３〜25重量％、亜鉛
及び錫から選ばれた金属の少なくとも一種を0.1
〜５重量％、及びアルミニウム及びシリコンから
選ばれた金属の少なくとも0.1〜１重量％含有す
る銅合金粉末、及び(ハ)有機錫化合物、チウラム類
及びジチオカルバミン酸塩から選ばれた少なくと
も一種の化合物からなる水中防汚塗料組成物。 ５ 展色剤は、ビニル樹脂、塩化ゴム樹脂、シリ
コンゴム、油性ワニス、ロジン、有機錫化合含有
ポリマーから選ばれた少なくとも一種である特許
請求の範囲第４項記載の水中防汚塗料組成物。 ６ 展色剤（固形分）100重量部に対し、銅合金
粉末100〜800重量部および化合物(ハ)250重量部以
下の割合からなる特許請求の範囲第４項又は第５
項記載の水中防汚塗料組成物。[Claims] 1. (a) a color vehicle, (d) 3 to 25% by weight of at least one metal selected from nickel and manganese, and at least one metal selected from zinc and tin.
An underwater antifouling paint composition comprising copper alloy powder containing 0.1 to 5% by weight, and 0.1 to 1% by weight of at least one metal selected from aluminum and silicon. 2. The underwater antifouling paint composition according to claim 1, wherein the color vehicle is at least one selected from vinyl resin, chlorinated rubber resin, silicone rubber, oil-based varnish, rosin, and organic tin compound-containing polymer. 3. The underwater antifouling paint composition according to claim 1 or 2, comprising 100 to 950 parts by weight of copper alloy powder to 100 parts by weight of color vehicle (solid content). 4 (a) Color vehicle, (d) 3 to 25% by weight of at least one metal selected from nickel and manganese, and 0.1% by weight of at least one metal selected from zinc and tin.
~5% by weight, and at least 0.1 to 1% by weight of a metal selected from aluminum and silicon, and (c) at least one compound selected from organotin compounds, thiurams, and dithiocarbamates. An underwater antifouling paint composition. 5. The underwater antifouling paint composition according to claim 4, wherein the color vehicle is at least one selected from vinyl resin, chlorinated rubber resin, silicone rubber, oil-based varnish, rosin, and organic tin compound-containing polymer. 6 Claims 4 or 5 consisting of 100 to 800 parts by weight of copper alloy powder and 250 parts by weight or less of compound (c) to 100 parts by weight of color vehicle (solid content)
The underwater antifouling paint composition described in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4491084A JPS60188480A (en) | 1984-03-09 | 1984-03-09 | Antifouling paint composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4491084A JPS60188480A (en) | 1984-03-09 | 1984-03-09 | Antifouling paint composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60188480A JPS60188480A (en) | 1985-09-25 |
| JPS6247912B2 true JPS6247912B2 (en) | 1987-10-09 |
Family
ID=12704615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4491084A Granted JPS60188480A (en) | 1984-03-09 | 1984-03-09 | Antifouling paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60188480A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4835050A (en) * | 1986-08-11 | 1989-05-30 | Clayton And Colleagues, Inc. | Antifouling paint compositions and method |
| JPH0220572A (en) * | 1988-07-07 | 1990-01-24 | Shinto Paint Co Ltd | Prevention of algae from growing in glass fiber-reinforced polyester cistern |
| CN109666243A (en) * | 2018-11-27 | 2019-04-23 | 盐城市瑞通塑胶有限公司 | A kind of PVC electric power protecting pipe and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58201862A (en) * | 1982-05-18 | 1983-11-24 | Bridgestone Corp | Antistaining material |
-
1984
- 1984-03-09 JP JP4491084A patent/JPS60188480A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58201862A (en) * | 1982-05-18 | 1983-11-24 | Bridgestone Corp | Antistaining material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60188480A (en) | 1985-09-25 |
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